JP2006151925A - Method for treating laver for various alga exterminating and disease control of laver and laver-treating agent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for treating laver, by which various sea weeds, such as diatoms and green laver, adhered to or mixed with cultured laver can be exterminated and various diseases caused by pathogenic microbes, such as SUMINORISHO (acicular bacteriosis) can effectively be controlled or prevented, and which reduces loads on ocean environments as much as possible, and to provide a laver-treating agent. <P>SOLUTION: This method for treating laver to exterminate various sea weeds on the laver and control various diseases of the laver, comprising using an electrolyzed solution (laver-treating agent) obtained by electrolyzing an organic acid seawater solution, is characterized in that the organic acid is at least one of organic acids having acid dissociation exponents (pKa) of ≥4. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to various algae including attached diatoms such as liquophora and tabellaria that grow on cultured seaweed, and bacteria such as needle-shaped bacteria that grow on the surface of laver leaf bodies and cause smolism In addition, it can effectively and effectively control bacteriomyopathy such as green spot disease, pseudo-scouring disease, red rot disease, and rod-shaped fungal disease that infects nori leaves and causes severe damage. The present invention relates to a laver treatment method and a laver treatment agent for controlling algae and controlling diseases for the purpose of cultivating fresh cultured laver.

2. Description of the Related Art Conventionally, cultured seaweed includes mosquitoes such as licomophora belonging to diatoms (Licomophora flavellate), tabellaria (Synedra sp.), Green algae (Enteromomoropha prolofera), and high-algae genus P. thaliana (E. compressa um). Bacterial fungi, red rot, fungus fungus (Olpidiopsis) genus fungus mold, and flavobacterium or Vibrio spp. Pathogenic fungi (sminori), green spot disease, There are many miscellaneous algae and diseases such as bacteriosis such as pseudo-squeezed diseases.
As a method for extermination and control of these algae and diseases, the tide tidal cycle is used to lift the laver net in the air for a certain period of time to dry, and the difference in resistance to drying of the algae and pathogens and laver is utilized. In addition, weed control and disease control are being carried out.

  However, it is difficult to eliminate miscellaneous algae and pathogens by drying the laver net in the solid culture that cannot be dried using tides. In addition, even in the column-type aquaculture that can perform the drying operation using tides, the disease control may not be completely possible only by the drying operation depending on the type or degree of the disease. As a solution to this problem, an acid treatment technique has been developed (see, for example, Patent Document 1) and is widely spread and used.

  The acid treatment technology currently in widespread use is a preparation that uses an organic acid as the main component and is used as a solution diluted to about pH 2 with in-situ seawater. However, it may be a problem if it causes an organic load on the marine environment. is there. In addition, there are miscellaneous algae and diseases that are difficult to control by these acid treatments.

In order to avoid and solve such current problems, research and development of environmentally friendly and highly effective processing technology has continued. There is an attempt to use an electrolysis solution as one of the directions. Both of them use electrolysis solution obtained by electrolyzing seawater or aqueous chloride solution for adhering diatoms of laver, extermination of attached bacteria, cleaning treatment etc. (for example, see Patent Documents 2 to 9), The current situation is that the technology has not yet been completed.
For this reason, there is an urgent need in the industry for practical use of a laver treatment technique that has the least impact on the marine environment and is highly effective.

On the other hand, while there is a promising technique of electrolytic sterilization, one of the main reasons why we have not succeeded in practical application of miscellaneous algae and miscellaneous bacteria treatment technology applying that technique in the seaweed culture field, It is considered that one of the causes is that the object to be treated is as large as a 1.8 m × 18 m laver net and the amount of organic matter is large.
When sterilizing and disinfecting using an electrolysis solution, the electrolysis solution is usually strongly acidic water generated in an anode chamber using a diaphragm type electrolytic cell. The diaphragm used in the electrolytic cell is a membrane with a delicate structure that allows certain ions and electrons generated by electrolysis to pass therethrough but prevents many molecules such as water from passing freely.

On the other hand, the seaweed net to be treated is large in volume and has a large amount of organic matter, and the algae to be removed and the seaweed that should not be damaged must coexist and must be selectively removed. There is a problem that sterilizing components such as the chlorine concentration of the electrolytic solution cannot be made too high.
For this reason, since a large amount of electrolyte is required for the treatment, it is preferable to repeatedly use the electrolyte instead of discarding it once. When the electrolytic solution treated with is circulated, in the diaphragm type electrolytic cell, the diaphragm is clogged and damaged, and it is difficult to make equipment.

A non-diaphragm type diaphragm is also known as an electrolysis method, but the non-diaphragm type is generally said to have poor sterilizing power. The reason for the low sterilizing power is considered to be the pH of the electrolyte. The diaphragm electrolyte is considered to be because the pH is weakly acidic to weakly alkaline although the free effective chlorine concentration is high. In order to make up for this drawback, non-diaphragm electrolyzed water added with hydrochloric acid has also been studied (for example, see Patent Documents 10 to 14).
However, when the solution to which hydrochloric acid is added is electrolyzed, the added hydrochloric acid is also electrolyzed, so that the pH fluctuates during the electrolysis and the sterilizing action is unstable.

It is also known to add various organic acids to the electrolyte solution in order to lower the pH of the electrolyte solution (see, for example, Patent Documents 15 to 18), but an acid having an acid dissociation index (pKa) of less than 4 For example, when lactic acid, malic acid, citric acid, tartaric acid, fumaric acid, etc. are used, substances with strong oxidizing power such as chlorine produced by electrolysis react with these highly ionized acids, and the redox potential of the electrolyte The effective chlorine concentration does not increase easily, and even if it increases once, when the application of electrolysis power is stopped, the redox potential and free effective chlorine concentration decrease rapidly, and the sterilizing electrolyte solution is stabilized. There is a problem that it cannot be supplied.
Japanese Patent Publication No.56-12601 JP 7-313007 A JP-A-8-140512 JP 2003-174828 A JP 2003-235373 A JP 2004-33195 A JP 2004-81186 A JP 200497042 A Japanese Patent Laid-Open No. 2004-155706 Japanese Examined Patent Publication No. 4-94785 Japanese Patent No. 2619756 Japanese Patent No. 2627100 JP-A-10-128336 JP-A-11-266733 JP-A-7-313982 Japanese Patent Application Laid-Open No. 8-299996 JP 10-314746 A JP 2003-170167 A

  The present invention is to solve this problem in view of the problems and current situation of the prior art described above, and includes various algae such as diatoms that grow on cultured seaweeds, various bacterial diseases such as sminoliosis. An object of the present invention is to provide a laver treatment method and a laver treatment agent that can effectively and efficiently control or prevent diseases, and that eliminate as much of the seaweed as possible and control diseases. .

  As a result of diligent studies to solve the above-described conventional problems, the present inventor obtained by electrolyzing seawater to which a specific organic acid was added as a means for controlling miscellaneous algae and controlling pests of cultured laver. The present inventors have found that the above-mentioned laver treatment method and laver treatment agent can be obtained by treating a laver net with an electrolyte having a specific property. Thus, the present invention has been completed.

That is, the present invention resides in the following (1) to (8).
(1) A laver treatment method for controlling algal miscellaneous algae and laver diseases using an electrolysis solution obtained by electrolyzing an organic acid seawater solution, wherein the organic acid has an acid dissociation index (PKa) A laver treatment method comprising at least one of four or more organic acids.
(2) The laver treatment method according to (1), wherein the organic acid is at least one selected from propionic acid, acetic acid, and succinic acid.
(3) The seaweed treatment method according to (1) or (2) above, wherein the pH of the organic acid seawater solution is in the range of 2 to 5.
(4) The laver treatment method according to any one of (1) to (3), wherein the electrolysis method is a non-diaphragm type in which no diaphragm is provided between the anode and the cathode.
(5) In any one of the above (1) to (4), the pH of the electrolysis solution is in the range of 3 to 5, the oxidation-reduction potential is 1140 mV or more, and the free effective chlorine concentration is 1 ppm or more. The seaweed processing method as described.
(6) A laver treatment method in which a laver net is treated by dipping or spraying using the electrolysis solution prepared under the conditions described in any one of (1) to (5) above.
(7) The electrolysis solution is prepared in an electrolysis tank installed on the seaweed work boat, and the laver net is treated in the treatment tank installed on the seaweed work boat. And circulate the electrolysis solution using a pump, and electrolysis is performed during the laver treatment to maintain the properties of the treatment solution described in (5) above.
(8) A laver treatment agent comprising an electrolysis solution prepared under the conditions described in any one of (1) to (5) above.

In the present invention, the term “seaweed treatment” refers to the elimination of moss, such as diatoms, which grow on cultured seaweed and inhibit the growth of seaweed or cause quality degradation. For the purpose of extermination, control, prevention, or nori activation of bacteria causing causative diseases, etc. and green spot disease, pseudo-scouring disease, etc., laver net is used as a treatment solution. It is said to be immersed or sprayed with a treatment solution.
Here, the above-mentioned “extermination of miscellaneous algae” means that algal species such as diatoms growing on or mixed with nori are selectively killed and removed. In addition, the term “control and control of pathogenic bacteria” means the sterilization and removal of bacteria causing causative bacteria that cause sminoliosis, as well as green spots, pseudo-squeezed diseases, etc. . Furthermore, “control or prevention of disease” means treatment of a laver disease or prevention of a laver from being affected by a disease. “Activation of seaweed” means improving the quality of seaweed growth, color of laver, gloss, and the like.
Further, in the present invention, the immersion (immersion) treatment means that the laver net on which the nori grows and grows is hand-rolled into the treatment tank using a roller or the like, or is immersed in the treatment liquid for a certain period of time or passed through the treatment liquid. Say. In addition, the spraying process is a seaweed processing ship (also called a diving ship) equipped with a propulsion device, or a ark that dives under the seaweed net to lift the seaweed net into the air and uses a shower or a spray nozzle etc. This means spraying the treatment liquid from below or above the net.

  According to the present invention, the attached diatom Taberaria, which was difficult to remove with conventional treatment agents, can be effectively eliminated, and harmful bacteria that cause Sminoriosis and the like can be effectively removed in a short time. In addition, a laver treatment method and a laver treatment agent are provided that can be eliminated and have less burden on the marine environment than conventional treatment agents.

Hereinafter, embodiments of the present invention will be described in detail.
The laver treatment method of the present invention is a laver treatment method for controlling laver weeds and nori disease using an electrolysis solution obtained by electrolyzing an aqueous solution of an organic acid, the organic acid Is composed of at least one organic acid having an acid dissociation index (pKa) of 4 or more.

In the present invention, an electrolyzed solution (stock solution) for preparing an electrolysis solution is composed of a seawater solution of an organic acid composed of at least one organic acid having an acid dissociation index (pKa) of 4 or higher, and has a pH of The thing in the range of 2-5 is desirable.
Organic acids that can be used are organic acids having an acid dissociation index (pKa) of 4 or higher, such as propionic acid (pKa4.87), acetic acid (pKa4.76), succinic acid (pKa4.21), butyric acid (pKa4.8). ), At least one (each alone or a mixture of two or more) such as valeric acid (pKa 4.8) caproic acid (pKa 4.8). Preferably, at least one of succinic acid, acetic acid, and propionic acid is desirable from the standpoint of ease of use with less off-flavors.
Acids having an acid dissociation index (pKa) of less than 4 (ionization constant exceeding 1 × 10 ⁴ ), such as lactic acid (pKa 3.86), malic acid (pKa 3.40), citric acid (pKa 3.16), tartaric acid ( When pKa3.06), fumaric acid (pKa3.02), etc. are used, substances with strong oxidizing power such as chlorine produced by electrolysis react with these highly ionized acids, and the redox potential of the electrolyte ( ORP) and free effective chlorine (ACC) concentrations do not increase easily, and even if they increase once, when the application of electrolytic power is stopped, the redox potential and free effective chlorine concentration decrease rapidly and have bactericidal activity The subject that electrolyte solution cannot be supplied stably arises and is not preferable.
In the present invention, when at least one organic acid having an acid dissociation index (pKa) of 4 or higher is used as the organic acid, the reactivity with the electrolytic solution is low, and the redox potential and the effective chlorine concentration decrease. Therefore, a stable electrolyte is supplied.

In addition, when compared with organic acids having an acid dissociation index (pKa) of 4 or more, such as succinic acid, acetic acid, and propionic acid, acetic acid is slightly more reactive, and succinic acid and propionic acid are almost equivalent and It is inferred that the reactivity is low. Comparing the other physical properties of these two organic acids, succinic acid has almost no volatility at room temperature, but acetic acid and propionic acid have high volatility, which causes odors at the site where the electrolyte is used. When used in a large amount as a laver treatment agent used under open conditions, the usability is slightly inferior. On the other hand, succinic acid has desirable properties in terms of stability of the electrolytic solution and non-volatility at room temperature, but its solubility in water is not so good. In this respect, when preparing a stock solution of an aqueous solution as an electrolytic aid, Inconvenient.
Therefore, in the present invention, from the viewpoint of further usability and the like, it is particularly preferable that succinic acid is a main component (50% by weight or more in the organic acid) and propionic acid and / or acetic acid is further contained. Thereby, an even more desirable electrolytic solution can be supplied.

  In the present invention, natural seawater can be used as a solvent for the electrolyte solution, and an appropriate amount (1 to 10% by weight) of an electrolyte component such as sodium chloride and calcium chloride may be added to the natural seawater. Artificial seawater composed of saline similar to seawater can also be used.

The pH of the electrolyte solution (stock solution) is preferably adjusted to a range of 2 to 5. The pH is adjusted depending on the type of organic acid used, the amount used, and the like. The concentration of the acid such as the organic acid is usually 0.01 to 0.5% by weight (0.00001 to 0.1 mol).
If the pH is less than ₂ , the content ratio of molecular chlorine (Cl ₂ ) in the electrolyte solution is increased, and the risk of chlorine gas generation is increased. Is not preferable.

In the present invention, the electrolysis solution (electrolytic solution) is an aqueous seawater solution in which an organic acid composed of at least one organic acid having an acid dissociation index (pKa) of 4 or higher is dissolved and the pH is in the range of 2 to 5. It is obtained by passing a direct current through an electrode (electrolyte) to an electrode comprising an anode and a cathode. The electrolysis method is preferably a non-diaphragm type in which no diaphragm is provided between the positive and negative electrodes from the viewpoint of ease of maintenance and management of the apparatus.
In order for the effect of the present invention to work more effectively, the obtained electrolysis solution may be acidic, but is preferably pH 3-5. When the pH of the electrolysis solution is less than 3, the chlorine compound in the electrolyte solution has a high molecular chlorine (Cl ₂ ) content ratio, which increases the risk of chlorine gas generation. If it exceeds, the ratio of hypochlorite ion (OCl ⁻ ) that is inferior in sterilizing power increases, and the algaecidal sterilizing effect decreases, which is not preferable. Therefore, it is preferable to set the pH within a range of 3 to 5 where the generation of harmful gas can be prevented and the ratio of hypochlorous acid (HOCl) having a high sterilizing and algicidal effect is high.
In addition, the oxidation-reduction potential (ORP) of the electrolyte used for laver treatment should be characterized by the occurrence of free effective chlorine concentration (ACC) of 1 ppm or more in an oxidized state of 1140 mV or more in terms of hydrogen electrode. The redox potential (ORP) is preferred. 1150 mv or more is desirable, more preferably 1150 to 1220 mv, and the effective chlorine concentration (ACC) is 3 ppm or more, more preferably 3 to 15 ppm.

  In the present invention, in order to maintain the pH and oxidation-reduction potential (OPR) state of the electrolysis solution in the above-mentioned range suitable for effective laver treatment, it is preferable that an acid solution in which new acid is dissolved even during laver treatment. It is desirable to continue application (energization) for replenishment and electrolysis. The acid solution is preferably replenished by using a feed pump linked to the pH meter as an index, and whether to continue the application by using the power supply device linked to the residual chlorine meter as an index of the free effective chlorine concentration. Alternatively, it is preferable to apply the oxidation-reduction potential as an index by a power supply device linked to the oxidation-reduction potentiometer.

In the present invention, the laver treatment agent (liquid) used in the treatment tank is composed of an electrolysis solution prepared so as to satisfy the above conditions. By immersing the cultured laver in the treatment tank containing the electrolyzed liquid (immersion method, immersion process) or by spraying the electrolyzed solution on the cultured laver (spraying method, spraying process) Is performed.
In these laver treatments, the time during which the electrolysis solution and the laver are in contact, that is, the treatment time varies depending on the properties of the prepared electrolyte, the target algae and pathogens, but between 1 second and 1 minute. It is preferable that it is preferably 5 seconds to 30 seconds.
After the treatment in the treatment tank, the laver net is immediately returned to seawater and normal aquaculture is continued.

In the present invention, the electrolysis of the organic acid seawater solution is performed in an electrolysis tank installed on a seaweed work boat, and the prepared electrolyte is treated similarly on the seaweed work boat using a circulation pump. It supplies to a tank and processes a laver in the said processing tank. A circulation pump is used between the electrolytic bath and the treatment bath, and the electrolytic solution is constantly circulated during operation. The electrolytic bath and the processing bath may be adjacent to each other or may be installed at different positions on the work boat and connected by a circulation pump or a circulation pipe.
As the electrode used in the electrolysis tank used in the present invention, carbon, platinum, palladium, iridium or the like is used for the anode, but platinum or a platinum-coated electrode is preferably used from the viewpoint of electrolytic efficiency. For the cathode, iron, stainless steel, titanium, or the like is used, but it is preferable to use stainless steel or titanium from the viewpoint of corrosion resistance and the like.

In the present invention, as a specific device for continuously performing the laver treatment, for example, a laver treatment device 20 mounted on the laver treatment vessel 10 shown in FIG. 1 can be used.
In the figure, 21 is a processing tank, 22 is an electrolytic solution storage tank, 23 is an electrolysis tank, 24 is an electrolytic acid stock solution storage tank, 25 is a pH controller, 26 is a free chlorine concentration controller or ORP controller, and 27 is an electrolytic solution. A replenishment pipe, 28 is an electrolyte recovery pipe, and 29 is a laver net.

The electrolyte used in the treatment tank 21 is an electrolyte obtained by electrolyzing a seawater solution of an organic acid composed of at least one organic acid having an acid dissociation index (pKa) of 4 or higher. The algae control effect and the control effect against diseased fungi such as needle-shaped bacteria are high, and these miscellaneous algae and disease fungi can obtain a control effect of almost 100% just by contacting the electrolyte for about 5 to 20 seconds. .
In this embodiment, it is possible to continuously carry out algae control and pest control of cultured seaweed in a short time. That is, if the processing ship having the structure of the system shown in FIG. 1 moves forward at a speed of about 10 to 20 m / min, the laver net 29 processed in the processing tank 21 starts from 5 seconds. Nori processing is performed in 30 seconds.

In the present invention, as shown in FIG. 1, the electrolytic solution used in the treatment tank 21 is prepared in an electrolysis tank 23 installed on the laver work vessel 10, and the set free effective chlorine concentration or reduction potential ( The electrolysis is continued in conjunction with the monitor's free chlorine concentration meter or oxidation-reduction potentiometer (free chlorine concentration controller or ORP controller 26) so as to maintain ORP. Further, it is desirable that the pH of the electrolytic solution is constantly adjusted to the set pH value by supplying the acid stock solution from the acid stock solution storage tank 24 for electrolysis by a feed pump linked to a pH meter (pH controller 25).
In addition, although the pH value fluctuation of the electrolyte solution does not affect the algicidal effect and the bactericidal effect, the concentration of the above-mentioned organic acid that affects the pH greatly affects the oxidation-reduction potential of the electrolyte solution, As a result, it affects the algicidal effect and the bactericidal effect, so it is desirable to adjust the pH constantly during operation.

For example, as shown in FIG. 1, the laver treatment work in the present invention can be performed while diving under a laver net 29 by a laver treatment ship 10. After the laver net 29 introduced into the processing tank 21 by the propulsion movement of the laver processing vessel 10 is immersed in the electrolytic solution, the laver net 29 moves in the air as the processing vessel 10 advances, and the rear of the processing vessel 10 It is returned to the sea level. During this time, if the traveling speed of the processing vessel is around 10 to 20 m / min and the length of the processing tank 21 in the vertical axis direction is 2 to 4 m, the immersion treatment time in the processing tank 21 is as short as 6 to 24 seconds. It will be time. In addition, the dimension of the vertical axis | shaft direction of the processing tank on a laver processing ship is about 2-4 m.
In the present invention, the electrolysis solution prepared under the above-described conditions is continuously supplied to the treatment tank 21, and the seaweed treatment can be performed by the immersion treatment or the spraying treatment.

  In the present invention configured as described above, weeds are removed from seaweed using an electrolysis solution obtained by electrolyzing a seawater solution of an organic acid composed of at least one organic acid having an acid dissociation index (pKa) of 4 or more. And laver disease control, rapid oxidation-reduction potential (ORP) and free effective chlorine concentration (ACC) increase during electrolysis, stable pH is obtained, and stable electrolyte is obtained. Even if 24 hours have passed since the application was stopped, the electrolyte solution has excellent stability, so it is possible to effectively remove the attached diatom tabellaria, which was difficult to remove with conventional treatment agents. In addition, a laver treatment method and a laver treatment agent capable of efficiently and continuously controlling pathogenic fungi such as sminoriosis in a short time and cultivating a healthy cultured laver can be obtained.

  Next, the present invention will be described in more detail with reference to test examples.

In the following Test Examples 1 to 3, a laver treatment apparatus having a treatment tank 1 (total capacity 4 liters) and an electrolysis tank (total capacity 1 liter) 2 serving as an electrolysis treatment apparatus shown in FIG. 2 was used. The DC current used for the electrolysis was supplied by a DC constant voltage / constant current power supply PR36-3A manufactured by Kenwood TMI. The electrolysis method was a diaphragm type, and the electrodes shown in Test Examples 1 to 3 below were used as the electrolysis electrodes. In order to prevent corrosion, the circulation pump 3 was a chemical pump that does not use metal in the liquid contact portion, and the circulation amount was such that the total amount of liquid was rotated once in 3 minutes.
ORP and pH were measured with a personal pH / ORP meter manufactured by Toko Chemical Co., and effective chlorine (ACC) was detected with "Rapid DPD reagent for residual chlorine measurement" manufactured by Kanto Chemical Co., Inc.

(Test Example 1)
Prepare several levels of seawater solution (electrolyte) for each of hydrochloric acid, succinic acid, acetic acid and propionic acid, electrolyze each, and change the properties of each electrolyte over time Evaluated.
In addition, using the electrolyte solution after 30 minutes from the start of application, an algae killing test of tabellaria and liquophora, which are adherent diatoms of seaweed, a bactericidal test of needle-shaped bacteria, and a toxicity test on laver leaf cell.
For the electrolysis, carbon was used for the anode, iron was used for the cathode, and the electrolysis power was 6 V × 0.35 A. The temperature of the electrolytic solution preparation and the laver leaf body treatment was 11 ° C.
These test results are shown in Tables 1 to 4 below.

Looking at the results in Table 1 above, in hydrochloric acid-added seawater, when the pH before electrolysis is 3.00, there is no significant change in pH due to electrolysis, and advantageous effective chlorine (ACC) is often generated, It was found that the algaecidal effect of diatoms is high. However, it was found that an electrolyzed solution having a pH of 4 or higher has a large pH increase and a low concentration of ACC, and the diatom algicidal effect and sterilization are remarkably inferior. This is probably because hydrochloric acid is also electrolyzed and the buffering action of hydrochloric acid is weak, resulting in a large pH fluctuation, and hence the diatom algae killing action is also weakened.
On the other hand, as is clear from the results of Tables 2 to 4, in the succinic acid electrolytic solution, the acetic acid electrolytic solution, and the propionic acid electrolytic solution, any of pH 3 to 5 has a slight pH change in the electrolytic solution, and The occurrence of ACC was also good. For this reason, it became clear that an electrolytic solution with high diatom algae killing effect and stable performance was produced.

(Test Example 2)
A seawater solution added with 0.05% by weight succinic acid and 0.05% by weight acetic acid, a seawater solution added with 0.007% by weight hydrochloric acid, 0.05% by weight succinic acid and 0.05% by weight propionic acid were added. Electrolyte solution to be electrolyzed consisting of seawater solution, 0.05% by weight of succinic acid, 0.025% by weight of acetic acid and 0.025% by weight of propionic acid. Changes in properties over time were evaluated. For the electrolysis, the electrolytic cell used in Example 1 was used. For the electrolysis, platinum was used for the anode, stainless steel was used for the cathode, and the electrolysis power was 6 V × 0.5 A. In addition, using the electrolyte solution after 30 minutes from the start of application, an algae killing test of tabellaria and liquophora, which are adherent diatoms of seaweed, a bactericidal test of needle-shaped bacteria, and a toxicity test on laver leaf cell.
The temperature of the electrolytic solution preparation and the laver leaf body treatment was 11 ° C.
These test results are shown in Tables 5 and 6 below.

Looking at the results in Tables 5 and 6 above, the electrolyte to which 0.05% by weight of succinic acid and 0.05% by weight of acetic acid were added, 0.05% by weight of succinic acid and 0.05% by weight of propionic acid were added. A seawater solution containing 0.05% by weight of succinic acid, 0.025% by weight of acetic acid and 0.025% by weight of propionic acid has a rapid redox potential (ORP) and free effective chlorine concentration ( An increase in ACC) was observed, and a stable electrolyte solution with a small pH fluctuation was obtained. The stability of the electrolytic solution was maintained even after 24 hours had elapsed after the application was stopped. For this reason, it became clear that an electrolytic solution with high diatom algae killing effect and stable performance was produced.
On the other hand, the electrolytic solution to which hydrochloric acid was added took a long time to increase ORP and ACC after application, and it took 20 minutes for the electrolytic solution to exhibit oxidizing power. Further, the pH increased from the time when the ORP became high, and a pH increase of 1.0 or more was observed 30 minutes after the application. This increase in pH continues even after the application is stopped, and after 24 hours, a further increase in pH of 0.5 or more is observed. In this test, an electrolyte solution with more stable performance can be obtained by adding succinic acid and acetic acid than hydrochloric acid. Generated.

(Test Example 3)
Electrolytic solution of seawater solution of monocarboxylic acid propionic acid, acetic acid, lactic acid, dicarboxylic acid succinic acid, malic acid, tartaric acid, fumaric acid, tricarboxylic acid citric acid, during application and after application stop Changes in properties over time were measured.
The concentration of each organic acid was 0.1%, 0.2%, and 0.4%, and electrolysis was performed using the experimental apparatus used in Test Examples 1 and 2. The electrolytic electrode used carbon for the anode and titanium for the cathode, and the electrolysis power was 6 V × 0.2 A. The electrolysis temperature was 11 ° C.
These test results are shown in Tables 7 to 9 below.

From the results shown in Tables 7 to 9, the oxidation-reduction potential (ORP) and free effective chlorine concentration (ACC) rise most rapidly after the start of application, and oxidation of these advantageous effective chlorine and the like is possible even in a high concentration acid solution. It was propionic acid and succinic acid that the material was produced and stably maintained. The acetic acid that showed similar properties was acetic acid, but in the case of acetic acid, it took time until the ORP increased and the ACC occurred when the concentration was high.
The acid dissociation indices (pKa) of propionic acid, succinic acid and acetic acid are 4.87, 4.21 and 4.76, respectively, and pKa is an acid of 4 or more.
On the other hand, in the low concentration electrolytes of lactic acid, malic acid, and tartaric acid, a certain increase in ORP and the occurrence of ACC are observed although the concentration is low. However, as the application time becomes longer, the ORP tends to decrease and shows a negative potential. In addition, this change continued or accelerated even when the application was stopped. Furthermore, ORP did not increase in these high-concentration liquids of organic acids, but decreased with application time. The acid dissociation indices (pKa) of these acids were 3.86, 3.40, and 3.06, respectively.
In addition, in fumaric acid and citric acid, the production of free effective chlorine was the least, and in particular, fumaric acid was not observed at all. Since there was little production of chlorine, the increase in ORP was low, and it reached only 1000 mV or more only in one period of the low concentration citric acid section. The dissociation index (pKa) of these acids was 3.02 for fumaric acid and 3.16 for citric acid.

  Summing up the above results, a nori treatment agent obtained by electrolyzing a seawater solution of an organic acid comprising at least one organic acid selected from succinic acid, acetic acid and propionic acid having an acid dissociation index (pKa) of 4 or higher is During electrolysis, a rapid increase in oxidation-reduction potential (ORP) and free effective chlorine concentration (ACC) was observed, and a stable electrolyte with a small pH fluctuation was obtained. Even so, the electrolyte solution has excellent stability, so it is possible to effectively remove the attached diatom tabellaria, which was difficult to remove with conventional treatment agents, and to treat diseases such as Sminori disease. It was found that a laver treatment method and a laver treatment agent that can control fungi efficiently and continuously in a short time and that can grow a healthy cultured laver are obtained.

It is an example of an embodiment of the present invention, and is a schematic diagram of a system showing a laver processing ship equipped with a laver processing apparatus used for a laver processing method. It is a top view which shows an example of the electrolysis production | generation apparatus used for a laver processing method.

Explanation of symbols

10 Nori treatment vessel 21 Treatment tank

Claims (8)

  A laver treatment method for controlling laver weeds and nori disease using an electrolysis solution obtained by electrolyzing a seawater solution of an organic acid, wherein the organic acid has an acid dissociation index (pKa) A laver treatment method comprising at least one of four or more organic acids.   The method for treating laver according to claim 1, wherein the organic acid is at least one selected from propionic acid, acetic acid, and succinic acid.   The seaweed treatment method according to claim 1 or 2, wherein the pH of the organic acid seawater solution is in the range of 2 to 5.   The laver treatment method according to any one of claims 1 to 3, wherein the electrolysis method is a non-diaphragm type in which no diaphragm is provided between the anode and the cathode.   The nori treatment method according to any one of claims 1 to 4, wherein the pH of the electrolysis solution is in the range of 3 to 5, the oxidation-reduction potential is 1140 mV or more, and the free effective chlorine concentration is 1 ppm or more.   A laver treatment method of treating a laver net by dipping or spraying using the electrolysis solution prepared under the conditions according to any one of claims 1 to 5.   The electrolysis solution is prepared in an electrolysis tank installed on the seaweed work boat, and the laver net is processed in the treatment tank installed on the seaweed work boat. The electrolysis tank and the treatment tank are pumps. The laver treatment method is characterized in that the electrolysis solution is circulated by using lye and electrolysis is performed to maintain the properties of the treatment solution according to claim 5 during the laver treatment.   It consists of an electrolysis solution prepared on the conditions as described in any one of Claims 1-5, The laver processing agent characterized by the above-mentioned.

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